CN105669924B - The organic inorganic hybridization block copolymer and its synthetic method of the structure containing POSS - Google Patents
The organic inorganic hybridization block copolymer and its synthetic method of the structure containing POSS Download PDFInfo
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- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
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- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
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- C08G2650/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group
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- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
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Abstract
The organic inorganic hybridization block copolymer and its synthetic method of the structure containing POSS, are related to block copolymer.The organic inorganic hybridization block copolymer of the structure containing POSS is denoted as PEG b P (POSS co DEA).Synthetic method：Poly glycol monomethyl ether, acid binding agent are dissolved in solvent and obtain poly glycol monomethyl ether solution, under condition of ice bath, 2- bromo isobutyl acylbromides are dissolved in solvent and are instilled again in poly glycol monomethyl ether solution after reaction, remove ice bath, it is reacted under normal temperature condition again, after obtained solution is dialysed with dialysis membrane, it is lyophilized to get macromole evocating agent；Gained macromole evocating agent, second comonomer, Third monomer are dissolved in solvent, after deaerating through continuous freeze thawing and catalyst being added under an argon, freeze thawing is further continued for deaerate and seal reaction after being filled with argon gas, liquid nitrogen frozen again, it after products therefrom removes catalyst by neutral alumina pillar, concentrates, precipitation, drying is to get block copolymer.
Description
Technical field
The present invention relates to block copolymers, more particularly, to a kind of organic inorganic hybridization block copolymer of structure containing POSS
And its synthetic method.
Background technology
Cage modle polyhedral oligomeric silsesquioxane (POSS) is a kind of novel organic-inorganic hybrid material occurred in recent years
The structural formula of material, POSS classics is (RSiO1.5) n (n >=4, R=H, alkyl, aryl or other organo-functional groups), between two
Silica (SiO2) and silicones (R2SiO) between n.Its cage modle skeleton has good dimensional stability and heat resistance, You Jiqu
Dai Ji also has designability.By the substituent group of design POSS, it is made to be copolymerized with monomer of different nature, it can be with composite structure
The abundant block copolymer with performance.
Amphiphilic copolymer be one kind in selective solvent, microphase-separated can occur, to form self-assembled structures
Polymer.It is self-assembly of abundant form, such as linear, spherical, vesica shape, stratiform, and has preferable controllability,
The thus research hotspot of always the field of polymers.Synthesis of amphoteric block copolymer main method is controllable/living polymerization at present,
The controllability of MOLECULE DESIGN can be achieved.
Silica forms cage structure in Polyhedral Oligomeric silsesquioxane (POSS), can be drawn POSS by MOLECULE DESIGN
Enter into polymer, prepares POSS based polyalcohols.In order to utilize its many excellent specific property, there are many people is embedding in POSS bases
A large amount of research work has been done in the synthesis of section copolymer.(W Zhang, B Fang, A Walther, the AHE M ü such as W Zhang
Ller.Macromolecules, 2009.42.2563-2569.) using amino POSS synthesize a kind of three thioesters chains of band POSS
Transfer agent, it includes POSS amphiphilic polymers that it is a kind of that acrylic acid synthesis, which is added, and has studied its self assembly behavior in water；
(Hussain H, Tan B H, Seah G L, et al.Langmuir, 2010,26 (14) such as Hussain H:11763-
11773.) bifunctional initiator is selected to synthesize polymethyl acyl using atom transfer radical polymerization (ATRP) method
Oxygen propyl group POSS- polyethylene glycol methacryloxypropyls POSS (P (MA-POSS)-b-PEG-b-P (MA-POSS)) ABA
Type block polymer.
Polymethylacrylic acid diethylamino ethyl ester (PDEA) is the water soluble polymer studied with apply relatively broad
One of, due to the presence of its tertiary amine group, PDEA is a kind of while poly- to pH value of solution, temperature sensitive stimuli-responsive height
Object.(Zeng J, Du P, Liu P.RSC Advances, 2013,3 (42) such as Zeng J:19492-19500.) select poly- second two
Alcohol macromole evocating agent, diethyl aminoethyl methacrylate (DEA) and crosslinking agent are using one pot process core crosslinking
Polymer, and have studied the drug release of polymer micelle.
What the simple block copolymer being copolymerized by PEG and POSS or random copolymer were self-assembly of in aqueous solution
Nano-micelle can not be as the carrier of transport and the control release of drug due to the lack of responsiveness.On the other hand simple to rely on
The substance and PEG of DEA or other responses are copolymerized to obtain block copolymer or random copolymer to be self-assembly of in aqueous solution
Nano-micelle, the macromolecular chain gap due to forming micella causes drug is unavoidable in transportational process in vivo to let out
Leakage.The block copolymer that the present invention synthesizes not only has response, but also since the cagelike structure of POSS groups can reduce medicine
The possibility that object is revealed in transportational process in vivo.
Invention content
The object of the present invention is to provide the organic inorganic hybridization of a kind of tool Thermo-sensitive and the structure containing POSS of pH responses is embedding
Section copolymer and its synthetic method.
The organic inorganic hybridization block copolymer of the structure containing POSS is denoted as PEG-b-P (POSS-co-DEA), knot
Structure formula is as follows：
Wherein, R=CH3Or H；R1=CH3, C2H5Or CH (CH3)2。
The synthetic route of the organic inorganic hybridization block copolymer of the structure containing POSS is as follows：
1) preparation of macromole evocating agent PEG-Br
2) synthesis of PEG-b-P (POSS-co-DEA)
Wherein, R=CH3Or H；R1=CH3, C2H5Or CH (CH3)2；M=135.
The synthetic method of the organic inorganic hybridization block copolymer of the structure containing POSS, includes the following steps：
1) synthesis of macromole evocating agent
Poly glycol monomethyl ether, acid binding agent are dissolved in solvent and obtain poly glycol monomethyl ether solution, it, will under condition of ice bath
2- bromo isobutyl acylbromides (BiBB) are dissolved in solvent instill in poly glycol monomethyl ether solution and react again after, remove ice bath, then
It reacts under normal temperature condition, after obtained solution is dialysed with dialysis membrane, is lyophilized to get macromole evocating agent, white powder；
In step 1), the average molecular weight of the poly glycol monomethyl ether can be 600,1000,2000,5000；It is described
Acid binding agent can be selected from one kind in triethylamine, pyridine etc.；One kind in dichloromethane, toluene etc. is steamed in the optional dead weight of solvent；
It is described 2- bromo isobutyl acylbromides (BiBB) are dissolved in the time for instilling in solvent and being reacted in poly glycol monomethyl ether solution again can be extremely
Few 2h；The time reacted under normal temperature condition can at least for 24 hours；The dialysis can dialyse reaction solution in deionized water
48h。
2) synthesis of block copolymer
Macromole evocating agent, second comonomer, Third monomer that step 1) obtains are dissolved in solvent, deaerated through continuous freeze thawing
And under an argon after addition catalyst, it is further continued for freeze thawing and deaerates and seal reaction, then liquid nitrogen frozen after being filled with argon gas, by gained
Product by neutral alumina pillar to remove catalyst after, concentrate, precipitation, dry organic nothing to get the structure containing POSS
Machine hybridized segmented copolymer is in pale yellow powder.
In step 2), the second comonomer can be selected from seven isobutyl group cagelike silsesquioxane of methacryloxypropyl
(MAPOSS), one kind in seven isobutyl group cagelike silsesquioxane (APOSS) of acryloxypropyl etc.；The Third monomer is optional
From diethyl aminoethyl methacrylate (DEA), methacrylic acid-N, N- dimethylamino ethyl ester (DMAEMA), (two is different by 2-
Propylcarbamic) one kind in ethyl methacrylate (DPA) etc.；The optional dead weight of solvent is steamed in tetrahydrofuran, toluene etc.
It is a kind of；It is described to polymerize after continuous freeze thawing degassing, can under protection of argon gas it polymerize after continuous freeze thawing deaerates 3~5 times；It is described anti-
The temperature answered can be 60~70 DEG C, and the time of reaction can at least for 24 hours；Anhydrous ether can be used as precipitating reagent repeatedly in the precipitation
Precipitation 2 times；Vacuum drying can be used in the drying.
The macromole evocating agent, the first monomer, second comonomer molar ratio can be (10~20): (50~100): (150
~300).
The present invention selects the poly glycol monomethyl ether synthetic macromolecule initiator PEG-Br of different molecular weight, with metering system
Monomethacryloxypropyl POSS and diethyl aminoethyl methacrylate (DEA) are successfully synthesized as comonomer using ATRP polymerization
The organic inorganic hybridization block copolymer PEG-b-P (POSS-co-DEA) of the structure containing POSS.
The target product of the present invention is the amphiphilic diblock copolymer of the structure containing POSS, and hydrophobic block is side group containing POSS
Arylate blocks, hydrophilic block is poly glycol monomethyl ether.Wherein diethyl aminoethyl methacrylate (DEA), first
Base acrylic acid-N, N- dimethylamino ethyl ester (DMAEMA), 2- (diisopropylaminoethyl) ethyl methacrylate (DPA) are with pH
Value or temperature change change its hydrophilic and hydrophobic, embody temperature or pH responses.The reaction uses ATRP polymerization method, controllability
It is good, can more easily synthesizing organic-inorganic hydridization block copolymer.
Description of the drawings
Fig. 1 is macromole evocating agent mPEG-Br's1H NMR spectras.In Fig. 1, abscissa is chemical shift chemical
shift(ppm)。
Fig. 2 is the organic inorganic hybridization block copolymer of the structure containing POSS, is denoted as PEG-b-P's (POSS-co-DEA)1H
NMR spectra.In fig. 2, abscissa is chemical shift chemical shift (ppm).
Fig. 3 is the infrared spectrum spectrogram of macromole evocating agent mPEG-Br.In figure 3, abscissa is wave number.
Fig. 4 is the organic inorganic hybridization block copolymer of the structure containing POSS, is denoted as the red of PEG-b-P (POSS-co-DEA)
External spectrum spectrogram.In Fig. 4, abscissa is wave number.
Specific implementation mode
The present invention is a kind of synthetic method of the organic inorganic hybridization block copolymer of the structure containing POSS.Specific implementation mode
It is shown in detail by following embodiment, but the present invention is not limited to following embodiments；The present invention can explain in other broader aspects, no
It is limited to these embodiments.
Embodiment 1
6g PEG, 2.2g TEA are dissolved in the DCM of 20ml.Reaction system is cooled to 0 DEG C with ice bath.It is added dropwise
The DCM mixed solutions of the BiBB and 2ml of 0.198ml.Recession, which is added dropwise, goes ice bath that system is made to be warmed to room temperature, and the reaction was continued for 24 hours.Reaction
Solution dialyses be lyophilized after 48h in deionized water, obtains white powder PEG-Br.Accordingly1H NMR spectras are as shown in Figure 1, IR
Spectrogram is as shown in Figure 3.
Weigh macromole evocating agent, measurement 0.233g second comonomers MAPOSS, 0.15mL that 0.4315g steps (1) obtain
Third monomer DEA, 0.015g ligand 2,2'- bipyridyls (Bpy) are dissolved in 1.5mL tetrahydrofurans.Metering is pressed than preparing PEG-
Br: MAPOSS: DEA=1: 5: 15 tetrahydrofuran solution systems, argon gas protection is lower after continuous freeze thawing deaerates 3~5 times is added
0.007g CuBr catalyst is further continued for continuous freeze thawing and deaerates 3~5 times, and reaction polymerize at 65 DEG C.Liquid nitrogen after the reaction set time
Sudden cold stopping reaction, response sample is by neutral alumina pillar to remove catalyst.Select anhydrous ether for precipitating reagent repeatedly
Centrifugation 2 times, vacuum drying obtain faint yellow block copolymer powder.Accordingly1H NMR spectras are as shown in Fig. 2, IR spectrograms
As shown in Figure 4.
Embodiment 2
Step 1 reaction time is 36h, remaining is the same as embodiment 1.
Embodiment 3
Step 2 prepares PEG-Br: MAPOSS: DEA=1: 3: 15 tetrahydrofuran solution systems, remaining is the same as embodiment 1.
Embodiment 4
Step 2 prepares PEG-Br: MAPOSS: DEA=1: 7: 15 tetrahydrofuran solution systems, remaining is the same as embodiment 1.
Embodiment 5
Step 2 prepares PEG-Br: MAPOSS: DEA=1: 9: 15 tetrahydrofuran solution systems, remaining is the same as embodiment 1.
Embodiment 6
Step 2 reaction time is 36h, remaining is the same as embodiment 1.
Embodiment 7
Step 2 reaction polymerize at 70 DEG C, remaining is the same as embodiment 1.
Embodiment 8
Step 2 prepares PEG-Br: MAPOSS: DMAEMA=1: 7: 15 tetrahydrofuran solution systems, remaining is the same as embodiment 1.
Embodiment 9
Step 2 prepares PEG-Br: MAPOSS: DPA=1: 7: 15 tetrahydrofuran solution systems, remaining is the same as embodiment 1.
Claims (10)
1. the organic inorganic hybridization block copolymer of the structure containing POSS, it is characterised in that it is denoted as PEG-b-P (POSS-co-DEA),
Its structural formula is as follows：
Wherein, R=CH3Or H；R1=CH3, C2H5Or CH (CH3)2；M=135, in the preparation process of block copolymer, addition
The molar ratio of POSS monomers and DEA are (50~100): (150~300).
2. the organic inorganic hybridization block copolymer of the structure containing POSS, synthetic route are as follows as described in claim 1
1) preparation of macromole evocating agent PEG-Br
2) synthesis of PEG-b-P (POSS-co-DEA)
Wherein, R=CH3Or H；R1=CH3, C2H5Or CH (CH3)2；M=135.
3. the synthetic method of the organic inorganic hybridization block copolymer of the structure containing POSS as described in claim 1, it is characterised in that
Include the following steps：
1) synthesis of macromole evocating agent
Poly glycol monomethyl ether, acid binding agent are dissolved in solvent and obtain poly glycol monomethyl ether solution, under condition of ice bath, by 2-
Bromo isobutyl acylbromide be dissolved in solvent instill again in poly glycol monomethyl ether solution react after, remove ice bath, then in normal temperature condition
Lower reaction after obtained solution is dialysed with dialysis membrane, is lyophilized to get macromole evocating agent, white powder；
2) synthesis of block copolymer
Macromole evocating agent, second comonomer, Third monomer that step 1) obtains are dissolved in solvent, through continuous freeze thawing deaerate and
After catalyst is added under argon atmospher, it is further continued for freeze thawing and deaerates and seal reaction, then liquid nitrogen frozen after being filled with argon gas, by the production of gained
Object by neutral alumina pillar to remove catalyst after, concentrate, precipitation, drying it is miscellaneous to get the organic-inorganic of the structure containing POSS
Change block copolymer, is in pale yellow powder.
4. the synthetic method of the organic inorganic hybridization block copolymer of the structure containing POSS as claimed in claim 3, it is characterised in that
In step 1), the average molecular weight of the poly glycol monomethyl ether is 600,1000,2000,5000.
5. the synthetic method of the organic inorganic hybridization block copolymer of the structure containing POSS as claimed in claim 3, it is characterised in that
In step 1), the one kind of the acid binding agent in triethylamine, pyridine.
6. the synthetic method of the organic inorganic hybridization block copolymer of the structure containing POSS as claimed in claim 3, it is characterised in that
In step 1), the solvent is selected from the one kind steamed in dichloromethane, toluene again；It is described 2- bromo isobutyl acylbromides are dissolved in it is molten
The time reacted in poly glycol monomethyl ether solution at least 2h is instilled in agent again；The time reacted under normal temperature condition is at least
24h；The dialysis is that reaction solution is dialysed 48h in deionized water.
7. the synthetic method of the organic inorganic hybridization block copolymer of the structure containing POSS as claimed in claim 3, it is characterised in that
In step 2), the macromole evocating agent, second comonomer, Third monomer molar ratio be (10~20): (50~100):
(150~300).
8. the synthetic method of the organic inorganic hybridization block copolymer of the structure containing POSS as claimed in claim 3, it is characterised in that
In step 2), the second comonomer is selected from seven isobutyl group cagelike silsesquioxane of methacryloxypropyl, acryloyl-oxy third
One kind in seven isobutyl group cagelike silsesquioxane of base；The Third monomer is selected from diethyl aminoethyl methacrylate, first
One kind in base acrylic acid-N, N- dimethylamino ethyl ester, 2- (diisopropylaminoethyl) ethyl methacrylate.
9. the synthetic method of the organic inorganic hybridization block copolymer of the structure containing POSS as claimed in claim 3, it is characterised in that
In step 2), the solvent is selected from the one kind steamed in tetrahydrofuran, toluene again；It is described to polymerize after continuous freeze thawing degassing, be
It polymerize under protection of argon gas after continuous freeze thawing deaerates 3~5 times.
10. the synthetic method of the organic inorganic hybridization block copolymer of the structure containing POSS as claimed in claim 3, it is characterised in that
In step 2), the temperature of the reaction is 60~70 DEG C, and the time of reaction is at least for 24 hours；The precipitation is made using anhydrous ether
For precipitating reagent repeated precipitation 2 times；It is described dry using vacuum drying.
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| CN102206315A (en) * | 2011-04-12 | 2011-10-05 | 厦门大学 | Polyhedron oligomerization sesquialter siloxane-based segmented copolymer and preparation method thereof |
| CN102443113A (en) * | 2011-11-01 | 2012-05-09 | 同济大学 | Preparation method of adjustable temperature-responsive star hybrid material using POSS as nucleus |
| CN103951804A (en) * | 2014-05-07 | 2014-07-30 | 厦门大学 | Polyhedral oligomeric silsesquioxane-based amphiphilic triblock copolymer and preparation method thereof |
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